CN101503858B - Preparation of solvent polyurethane finishing agent - Google Patents
Preparation of solvent polyurethane finishing agent Download PDFInfo
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- CN101503858B CN101503858B CN 200910095449 CN200910095449A CN101503858B CN 101503858 B CN101503858 B CN 101503858B CN 200910095449 CN200910095449 CN 200910095449 CN 200910095449 A CN200910095449 A CN 200910095449A CN 101503858 B CN101503858 B CN 101503858B
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Abstract
The invention discloses a method for preparing a solvent type polyurethane finishing agent, which comprises three steps: primary polycondensation, wherein dimethylol propionic acid, polylol, isocyanate and antioxidizer are mixed, fully stirred, and added with a catalyst for reaction at the temperature of between 60 and 80 DEG C until the viscocity of the material at 25 DEG C is between 180,000 and 250,000 centipoises to form prepolymer; secondary polycondensation, wherein the prepolymer is added with a diluents for dilution, and then added with the isocyanate for reaction at the temperature of between 60 and 80 DEG C until the viscocity of the material at 25 DEG C is between 180,000 and 250,000 centipoises to form polymer; chain extension, wherein the polymer is added with a chain extender for reaction at the temperature of between 60 and 90 DEG C until the viscocity of the material at 25 DEG C is between 180,000 and 250,000 centipoises, and the solvent type polyurethane finishing agent finished product is obtained after cooling. Through the proposal, the novel solvent type polyurethane finishing agent has the advantages of good water resistance, high water vapor permeability and the like.
Description
Technical field
The present invention relates to a kind of preparation method of fabric coating finishing composition, more specifically is a kind of preparation method of solvent polyurethane finishing agent.
Background technology
The fabric coating finishing composition claims again coating adhesive, is a kind of macromolecule compound of evenly coating fabric face.It forms one or more layers film by adhesive effect at fabric face, can not only improve the look and feel of fabric, and can increase the function of fabric, makes fabric have waterproof, water pressure resistance, ventilating and moisture-permeable, the specific functions such as inflaming-retarding antifouling and shading reflection.
Main application is polyacrylate(s) and polyurethanes at present.Polyurethane coating glue (Polyurethane is called for short PU).The urethane full name is polyurethane(s), is to contain in the molecular structure-macromolecular compound of NHCOO-unit, and this unit is formed by isocyanato and hydroxyl reaction, and reaction formula is as follows :-N=C=O+HO
-→-NH-COO
-
State Intellectual Property Office 2008 5 days 21 disclosed " preparation method of environment-friendly watersoluble polyurethane textile softening agent " (CN101182681), the preparation method of the watersoluble polyurethane textile softening agent of this patent literature: generate end group with vulcabond and dibastic alcohol compound first and be-performed polymer of NCO, then use dimethylol propionic acid and chainextender chain extending reaction, regulate the pH value to neutrality with triethylamine at last, add deionized water and stirring, namely obtain watersoluble polyurethane textile softening agent, the concrete technology step of described method is: in the reaction vessel of belt stirrer, add diatomic alcohol compounds and vulcabond, 80-85 ℃ of reaction 1.5-2 hour, be cooled to 70-75 ℃, add dimethylol propionic acid and chainextender, insulated and stirred 30-40min, dropping accounts for the dibutyl tin dilaurate of vulcabond weight 0.08-0.12%, add the acetone that accounts for total system weight 8-12% weight percent and reduce system viscosity, 60-65 ℃ of insulation 4.5 hours-5 hours, be down to room temperature, add in the triethylamine and after, add deionized water, stir, slough acetone, namely obtain watersoluble polyurethane textile softening agent, described each raw material reacts according to following proportioning :-NCO :-OH=2-4: 1 mol ratio, wherein-NCO represents isocyanate group,-OH represents the hydroxyl of dibastic alcohol compound, the mol ratio of dimethylol propionic acid and dibastic alcohol compound is 0.4-1.2: 1, and the mol ratio of chainextender and dibastic alcohol compound is 1-2.5: 1.This soft finishing agent can be applied in the spinning post-finishing, improves the softness of fabric, and draping property is given the fabric solid sense.But aforesaid method makes watersoluble polyurethane textile softening agent, and the fabric after processing is treated in raising especially at aspects such as water resistance, water vapour permeabilities.
Summary of the invention
For above-mentioned situation, the problem that quasi-solution of the present invention is determined provides the preparation method of a kind of water resistance, solvent borne polyurethane finishing composition that water vapour permeability is good
For the present invention that achieves the above object has adopted following technical scheme: a kind of preparation method of solvent borne polyurethane finishing composition, it comprises a polycondensation, secondary polycondensation, three steps of chain extension:
A a: polycondensation: dimethylol propionic acid, polyvalent alcohol, isocyanic ester and oxidation inhibitor mix, after fully stirring, add catalyzer, under 60-80 ℃ environment, react, to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, be that polymerization reaction take place generates the performed polymer that contains end-NCO group between isocyanic ester and the polyvalent alcohol, described dimethylol propionic acid, polyvalent alcohol, the mass ratio of dimethylformamide and isocyanic ester is 1: 50-80: 15-20, the add-on of described oxidation inhibitor is that the add-on of the described catalyzer of 4-9% of dimethylol propionic acid quality is the 0.1-2% of dimethylol propionic acid quality
Described polyvalent alcohol is that carbonatoms is the polyvalent alcohol of 2-4, and described oxidation inhibitor is phenol oxidation inhibitor, and described catalyzer is organo-bismuth class catalyzer or stanniferous class catalyzer;
B: secondary polycondensation: in performed polymer, add thinner performed polymer diluted, and then add different hydrogen acid ether, under 60-80 ℃ environment, react, to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, obtain polymer; The add-on of described thinner is the 12-18% of performed polymer quality, and the add-on of described different hydrogen acid ether is the 0.3-3% of performed polymer quality, and described thinner is toluene or butanone;
C: chain extension: in polymer, add chainextender, environment reaction at 60-90 ℃, to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, obtain solvent borne polyurethane finishing composition finished product after the cooling, the add-on of described chainextender is the 8-12% of polymer quality, and described chainextender is methyl ethyl ketone or di-alcohols chainextender and binary amine compound chainextender.
As improvement, described step a: in the polycondensation, also comprise dimethylformamide with dimethylol propionic acid, polyvalent alcohol, isocyanic ester and oxidation inhibitor mix simultaneously, the add-on of described dimethylformamide be the dimethylol propionic acid quality 35-50 doubly.
As improvement, the performed polymer that described step a obtains is also processed, namely step a being obtained adding again in the performed polymer isocyanic ester dilutes, under 60-80 ℃ environment, react, to viscosity 18-25 ten thousand centipoises of material 25 ℃ the time, the add-on of described isocyanic ester is the 10-15% that step a obtains the performed polymer quality.
The preparation method of above-mentioned solvent borne polyurethane finishing composition, described polyvalent alcohol is a kind of of ethylene glycol or glycerol or Isosorbide-5-Nitrae butyleneglycol or the miscellany more than any two.Described phenol oxidation inhibitor is antioxidant BHT or tri-butyl-phenol oxidation inhibitor or o-tert-butylphenol antioxidant 1010.Described organo-bismuth class catalyzer is methylsulphonic acid bismuth or Bismuth Octoate or vitamin P bismuth; Described tin class catalyzer is stannous octoate.Described di-alcohols chainextender is ethylene glycol, BDO, glycol ether, 1, the 6-hexylene glycol; Described binary amine chainextender is 3,3-, two chloro-4, the poly-di-amine of 4-diphenylmethanediamiand or 3,3-, two chloro-or 4,4-diphenylmethanediamiand or benzidine or triazinediamine.
Owing to having adopted such scheme, the present invention to adopt the new polyurethane finishing composition, form the continuity nonporous film at fabric face, contain on hydrophilic radical or the molecular backbone chain in this new polyurethane coating-forming agent and be embedded with hydrophilic segment, as-OH ,-NHCOO-,-SO
3H ,-COOH etc., intermolecular forces are very strong, and after the coating, solvent evaporates forms nonporous film, and novel synthetic method causes it to have good film-forming properties, can form tough and tensile and durable film at fabric, and waterproof and water-wash resistance are good." chemical ladder stone " effect of hydrophilic radical is that one side moves to low humidity one side to water vapour molecule along ladder from high humidity; PU forms by soft section and hard section on the other hand, forms respectively indefiniteness district and crystallizing field in the structure, because the unformed area molecular chain is more open, structure is not tight, and molecule easily enters, and migration and diffusion, thereby reaches wet purpose.Therefore water resistance is fine, and water vapour permeability is also very high.Particularly in polycondensation, add the functional monomer dimethylformamide, make above-mentioned performance more obvious.
Embodiment
The preparation method of solvent borne polyurethane finishing composition of the present invention comprises a polycondensation, secondary polycondensation, three steps of chain extension, is specially:
One, a polycondensation, the preparation of performed polymer.
Raw material is introduced:
1, commercially available dimethylol propionic acid
2, polyvalent alcohol: carbonatoms is the polyvalent alcohol of 2-4, can be a kind of of ethylene glycol or glycerol or Isosorbide-5-Nitrae butyleneglycol or the miscellany more than any two.
3, commercially available isocyanic ester
4, oxidation inhibitor: generally adopt phenol oxidation inhibitor, such as antioxidant BHT or tri-butyl-phenol oxidation inhibitor or o-tert-butylphenol antioxidant 1010.
5, catalyzer: machine bismuth class catalyzer or tin class catalyzer, all can such as methylsulphonic acid bismuth, Bismuth Octoate, vitamin P bismuth, stannous octoate.
6, commercially available dimethylformamide.
Concrete operation step
A certain amount of dimethylol propionic acid, polyvalent alcohol, isocyanic ester and oxidation inhibitor are mixed, after fully stirring, add catalyzer, under 60-80 ℃ environment, react, regularly the viscosity of reactant is tested (as every 3 minutes), to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises (viscosity of concrete material during at 25 ℃ can be controlled in 180,000 centipoises or 250,000 centipoises or 200,000 centipoises or 170,000 centipoises or 230,000 centipoises), make performed polymer, namely polymerization reaction take place generates the performed polymer that contains end-NCO group between isocyanic ester and the polyvalent alcohol.In above-mentioned steps, also can comprise dimethylformamide with dimethylol propionic acid, polyvalent alcohol, isocyanic ester and oxidation inhibitor mix simultaneously.
The adding quality of concrete each raw material and temperature of reaction control see the following form:
Two, secondary polycondensation, polymeric preparation
Secondary polycondensation concrete steps
Get the performed polymer that makes in a certain amount of above-mentioned steps, add toluene or butanone; Performed polymer is diluted, and then add different hydrogen acid ether, under 60-80 ℃ environment, react, regularly the viscosity of reactant is tested (as every 3 minutes), to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises (viscosity of concrete material during at 25 ℃ can be controlled in 180,000 centipoises or 250,000 centipoises or 200,000 centipoises or 170,000 centipoises or 230,000 centipoises), obtain polymer.
The adding quality of concrete each raw material and temperature of reaction control see the following form:
| Embodiment | Performed polymer | Toluene | Butanone | Isocyanic ester | Temperature of reaction | Polymerization effect |
| 1 | 1 kilogram | 0.12 kilogram | 0 | 0.003 kilogram | 60℃ | Better |
| 2 | 1 kilogram | 0.15 kilogram | 0 | 0.01 kilogram | 80℃ | Good |
| 3 | 1 kilogram | 0.18 kilogram | 0 | 0.03 kilogram | 70℃ | Better |
| 4 | 1 kilogram | 0 | 0.12 kilogram | 0.003 kilogram | 65℃ | Better |
| 5 | 1 kilogram | 0 | 0.15 kilogram | 0.01 kilogram | 75℃ | Good |
| 6 | 1 kilogram | 0 | 0.18 kilogram | 0.03 kilogram | 76℃ | Better |
The processing of performed polymer
As improvement, can before the secondary polycondensation, also process performed polymer first, namely obtaining adding again in the performed polymer isocyanic ester a polycondensation dilutes, reaction under 60-80 ℃ the environment (specifically can under 60 ℃ or 80 ℃ or 65 ℃ or 75 ℃ of temperature environments, carry out), to the viscosity 18-25 ten thousand of material 25 ℃ the time (viscosity of concrete material during at 25 ℃ can be controlled in 180,000 centipoises or 250,000 centipoises or 200,000 centipoises or 170,000 centipoises or 230,000 centipoises), the add-on of described isocyanic ester is 10% or 12% or 5% of performed polymer quality, obtain treated performed polymer, then carry out the secondary polycondensation such as last paragraph.
Three, chain extension, the preparation of solvent borne polyurethane finishing composition finished product
The introduction of chainextender
Chainextender of the present invention is methyl ethyl ketone or di-alcohols chainextender and binary amine compound chainextender.The di-alcohols chainextender is ethylene glycol, BDO, glycol ether, 1, the 6-hexylene glycol; Described binary amine chainextender is 3,3-, two chloro-4, the poly-di-amine of 4-diphenylmethanediamiand or 3,3-, two chloro-or 4,4-diphenylmethanediamiand or benzidine or triazinediamine.
Concrete operation step
Get the polymer that makes in a certain amount of above-mentioned steps, add chainextender, under 60-90 ℃ environment, react, regularly the viscosity of reactant is tested (as every 3 minutes), to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, obtain solvent borne polyurethane finishing composition finished product after the cooling.The adding quality of concrete each raw material, temperature of reaction control and product salient features see the following form:
| Embodiment | Polymer | Chainextender | Temperature of reaction | Viscosity in the time of 25 ℃ | Water resistance | Water vapour permeability |
| 1 | 1 kilogram | 0.12 kilogram | 60℃ | 180,000 centipoises | Better | Good |
| 2 | 1 kilogram | 0.08 kilogram | 80℃ | 250,000 centipoises | Better | Good |
| 3 | 1 kilogram | 0.10 kilogram | 70℃ | 200,000 centipoises | Good | Good |
| 4 | 1 kilogram | 0.11 kilogram | 85℃ | 220,000 centipoises | Good | Better |
| 5 | 1 kilogram | 0.09 kilogram | 90℃ | 230,000 centipoises | Good | Better |
Claims (6)
1. the preparation method of a solvent borne polyurethane finishing composition is characterized in that it comprises a polycondensation, secondary polycondensation, three steps of chain extension:
A a: polycondensation: dimethylol propionic acid, polyvalent alcohol, isocyanic ester and oxidation inhibitor mix, after fully stirring, add catalyzer, under 60-80 ℃ environment, react, to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, be that polymerization reaction take place generates the performed polymer that contains end-NCO group between isocyanic ester and the polyvalent alcohol, described dimethylol propionic acid, the mass ratio of polyvalent alcohol and isocyanic ester is 1: 50-80: 15-20, the add-on of described oxidation inhibitor is the 4-9% of dimethylol propionic acid quality, the add-on of described catalyzer is the 0.1-2% of dimethylol propionic acid quality
Described polyvalent alcohol is that carbonatoms is the polyvalent alcohol of 2-4, and described oxidation inhibitor is phenol oxidation inhibitor, and described catalyzer is organo-bismuth class catalyzer or tin class catalyzer;
B: secondary polycondensation: in performed polymer, add thinner performed polymer diluted, and then add isocyanic ester, under 60-80 ℃ environment, react, to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, obtain polymer; The add-on of described thinner is the 12-18% of performed polymer quality, and the add-on of described isocyanic ester is the 0.3-3% of performed polymer quality, and described thinner is toluene or butanone;
C: chain extension: in polymer, add chainextender, environment reaction at 60-90 ℃, to the viscosity of material 25 ℃ the time be 18-25 ten thousand centipoises, obtain solvent borne polyurethane finishing composition finished product after the cooling, the add-on of described chainextender is the 8-12% of polymer quality, described chainextender is di-alcohols chainextender and binary amine compound chainextender
Described step a: in the polycondensation, also comprise dimethylformamide with dimethylol propionic acid, polyvalent alcohol, isocyanic ester and oxidation inhibitor mix simultaneously, the add-on of described dimethylformamide be the dimethylol propionic acid quality 35-50 doubly.
2. the preparation method of solvent borne polyurethane finishing composition according to claim 1, it is characterized in that the performed polymer that described step a obtains is also processed, namely step a being obtained adding again in the performed polymer isocyanic ester dilutes, under 60-80 ℃ environment, react, to viscosity 18-25 ten thousand centipoises of material 25 ℃ the time, the add-on of described isocyanic ester is the 10-15% that step a obtains the performed polymer quality.
3. the preparation method of solvent borne polyurethane finishing composition according to claim 1 is characterized in that described polyvalent alcohol is a kind of of ethylene glycol or glycerol or BDO or the miscellany more than any two.
4. the preparation method of solvent borne polyurethane finishing composition according to claim 1 is characterized in that described phenol oxidation inhibitor is antioxidant BHT or tri-butyl-phenol oxidation inhibitor.
5. the preparation method of solvent borne polyurethane finishing composition according to claim 1 is characterized in that described organo-bismuth class catalyzer is methylsulphonic acid bismuth or Bismuth Octoate; Described tin class catalyzer is stannous octoate.
6. the preparation method of solvent borne polyurethane finishing composition according to claim 1 is characterized in that described di-alcohols chainextender is ethylene glycol, BDO, glycol ether, 1, the 6-hexylene glycol; Described binary amine chainextender is 3,3 '-two chloro-4, and 4 '-diphenylmethanediamiand or 3,3 '-two chloro-gather di-amine or 4,4 '-diphenylmethanediamiand or benzidine or triazinediamine.
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|---|---|---|---|
| CN 200910095449 CN101503858B (en) | 2009-01-14 | 2009-01-14 | Preparation of solvent polyurethane finishing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910095449 CN101503858B (en) | 2009-01-14 | 2009-01-14 | Preparation of solvent polyurethane finishing agent |
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| CN101503858A CN101503858A (en) | 2009-08-12 |
| CN101503858B true CN101503858B (en) | 2013-03-06 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912680A (en) * | 1972-05-04 | 1975-10-14 | Bayer Ag | Light fast polyurethane urea coating solutions |
| CN1418900A (en) * | 2002-12-05 | 2003-05-21 | 武汉大学 | Process for preparing water-based polyurethane powder material |
| CN101100500A (en) * | 2006-07-07 | 2008-01-09 | 习智华 | Polyurethane shape memory macromolecule material and synthetic technique thereof |
| CN101182681A (en) * | 2007-11-08 | 2008-05-21 | 华明扬 | Preparation method of environment-friendly watersoluble polyurethane textile softening agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4452139B2 (en) * | 2004-07-28 | 2010-04-21 | 日華化学株式会社 | Method for manufacturing leather materials |
-
2009
- 2009-01-14 CN CN 200910095449 patent/CN101503858B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912680A (en) * | 1972-05-04 | 1975-10-14 | Bayer Ag | Light fast polyurethane urea coating solutions |
| CN1418900A (en) * | 2002-12-05 | 2003-05-21 | 武汉大学 | Process for preparing water-based polyurethane powder material |
| CN101100500A (en) * | 2006-07-07 | 2008-01-09 | 习智华 | Polyurethane shape memory macromolecule material and synthetic technique thereof |
| CN101182681A (en) * | 2007-11-08 | 2008-05-21 | 华明扬 | Preparation method of environment-friendly watersoluble polyurethane textile softening agent |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-36960A 2006.02.09 |
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